TY - JOUR
T1 - Enhancing and Extinguishing the Different Emission Features of 2D (EA1−xFAx)4Pb3Br10 Perovskite Films
AU - Kennard, Rhiannon M.
AU - Dahlman, Clayton J.
AU - Morgan, Emily E.
AU - Chung, Juil
AU - Cotts, Benjamin L.
AU - Kincaid, Joseph R.A.
AU - DeCrescent, Ryan A.
AU - Stone, Kevin H.
AU - Panuganti, Shobhana
AU - Mohtashami, Yahya
AU - Mao, Lingling
AU - Schaller, Richard D.
AU - Salleo, Alberto
AU - Kanatzidis, Mercouri G.
AU - Schuller, Jon A.
AU - Seshadri, Ram
AU - Chabinyc, Michael L.
N1 - Funding Information:
The authors gratefully acknowledge Dr. Guang Wu of UCSB for single crystal XRD measurements, Dr. Alexander Mikhailovsky and Sepanta Assadi for additional optical measurements, and Dr. Naveen Venkatesan for assistance with simulation of GIWAXS patterns. Growth and structural characterization were supported by the US Department of Energy, Office of Science, Basic Energy Sciences, under Award Number DE‐SC‐0012541. Support of optical characterization was provided by Quantum Materials for Energy Efficient Neuromorphic Computing, an Energy Frontier Research Center funded by the US Department of Energy (DOE), Office of Science, Basic Energy Sciences, (BES), under Award Number DE‐SC0019273. Time‐resolved spectroscopy capabilities were supported by DURIP ARO grant 66886LSRIP. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE‐AC02‐76SF00515. The research reported here also made use the shared facilities of the UCSB MRSEC (National Science Foundation DMR 1720256), a member of the Materials Research Facilities Network ( www.mrfn.org ). R.M.K. gratefully acknowledges the National Defense Science and Engineering Graduate fellowship for financial support, E.E.M. gratefully acknowledges the NSF Graduate Research Fellowship Program under award number 2139319, and J.R.A.K. gratefully acknowledges the National Science Foundation Graduate Research Fellowship under Grant No. 1650114. S.P. gratefully acknowledges support from the Ryan Fellowship and the NSF Graduate Research Fellowship Program under Grant No. DGE‐1842165.
Funding Information:
The authors gratefully acknowledge Dr. Guang Wu of UCSB for single crystal XRD measurements, Dr. Alexander Mikhailovsky and Sepanta Assadi for additional optical measurements, and Dr. Naveen Venkatesan for assistance with simulation of GIWAXS patterns. Growth and structural characterization were supported by the US Department of Energy, Office of Science, Basic Energy Sciences, under Award Number DE-SC-0012541. Support of optical characterization was provided by Quantum Materials for Energy Efficient Neuromorphic Computing, an Energy Frontier Research Center funded by the US Department of Energy (DOE), Office of Science, Basic Energy Sciences, (BES), under Award Number DE-SC0019273. Time-resolved spectroscopy capabilities were supported by DURIP ARO grant 66886LSRIP. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515. The research reported here also made use the shared facilities of the UCSB MRSEC (National Science Foundation DMR 1720256), a member of the Materials Research Facilities Network (www.mrfn.org). R.M.K. gratefully acknowledges the National Defense Science and Engineering Graduate fellowship for financial support, E.E.M. gratefully acknowledges the NSF Graduate Research Fellowship Program under award number 2139319, and J.R.A.K. gratefully acknowledges the National Science Foundation Graduate Research Fellowship under Grant No. 1650114. S.P. gratefully acknowledges support from the Ryan Fellowship and the NSF Graduate Research Fellowship Program under Grant No. DGE-1842165.
Publisher Copyright:
© 2022 Wiley-VCH GmbH.
PY - 2022/9/5
Y1 - 2022/9/5
N2 - 2D hybrid perovskites are attractive for optoelectronic devices. In thin films, the color of optical emission and the texture of crystalline domains are often difficult to control. Here, a method for extinguishing or enhancing different emission features is demonstrated for the family of 2D Ruddlesden–Popper perovskites (EA1−xFAx)4Pb3Br10 (EA = ethylammonium, FA = formamidinium). When grown from aqueous hydrobromic acid, crystals of (EA1−xFAx)4Pb3Br10 retain all the emission features of their parent compound, (EA)4Pb3Br10. Surprisingly, when grown from dimethylformamide (DMF), an emission feature, likely self-trapped exciton (STE), near 2.7 eV is missing. Extinction of this feature is correlated with DMF being incorporated between the 2D Pb-Br sheets, forming (EA1−xFAx)4Pb3Br10∙(DMF)y. Without FA, films grown from DMF form (EA)4Pb3Br10, retain little solvent, and have strong emission near 2.7 eV. Slowing the kinetics of film growth strengthens a different emission feature, likely a different type of STE, which is much broader and present in all compositions. Films of (EA1−xFAx)4Pb3Br10∙(DMF)y have large, micron-sized domains and homogeneous orientation of the semiconducting sheets, resulting in low electronic disorder near the absorption edge. The ability to selectively strengthen or extinguish different emission features in films of (EA1−xFAx)4Pb3Br10∙(DMF)y reveals a pathway to tune the emission color in these compounds.
AB - 2D hybrid perovskites are attractive for optoelectronic devices. In thin films, the color of optical emission and the texture of crystalline domains are often difficult to control. Here, a method for extinguishing or enhancing different emission features is demonstrated for the family of 2D Ruddlesden–Popper perovskites (EA1−xFAx)4Pb3Br10 (EA = ethylammonium, FA = formamidinium). When grown from aqueous hydrobromic acid, crystals of (EA1−xFAx)4Pb3Br10 retain all the emission features of their parent compound, (EA)4Pb3Br10. Surprisingly, when grown from dimethylformamide (DMF), an emission feature, likely self-trapped exciton (STE), near 2.7 eV is missing. Extinction of this feature is correlated with DMF being incorporated between the 2D Pb-Br sheets, forming (EA1−xFAx)4Pb3Br10∙(DMF)y. Without FA, films grown from DMF form (EA)4Pb3Br10, retain little solvent, and have strong emission near 2.7 eV. Slowing the kinetics of film growth strengthens a different emission feature, likely a different type of STE, which is much broader and present in all compositions. Films of (EA1−xFAx)4Pb3Br10∙(DMF)y have large, micron-sized domains and homogeneous orientation of the semiconducting sheets, resulting in low electronic disorder near the absorption edge. The ability to selectively strengthen or extinguish different emission features in films of (EA1−xFAx)4Pb3Br10∙(DMF)y reveals a pathway to tune the emission color in these compounds.
KW - 2D halide perovskites
KW - crystals
KW - emission
KW - exciton–phonon coupling
KW - self-trapped excitons
KW - solvents
KW - thin films
UR - http://www.scopus.com/inward/record.url?scp=85131712586&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85131712586&partnerID=8YFLogxK
U2 - 10.1002/adom.202200547
DO - 10.1002/adom.202200547
M3 - Article
AN - SCOPUS:85131712586
SN - 2195-1071
VL - 10
JO - Advanced Optical Materials
JF - Advanced Optical Materials
IS - 17
M1 - 2200547
ER -